4-exomethylene-3-(hydroxy)[(3,4-methylenedioxy)phenyl]methyltetrahydrofuran

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 4-exomethylene-3-(hydroxy)[(3,4-methylenedioxy)phenyl]methyltetrahydrofuran
• 英文别名: (Alphar)-alpha-[(3R)-4-Methylenetetrahydrofuran-3-yl]-1,3-benzodioxole-5-methanol；(R)-1,3-benzodioxol-5-yl-[(3R)-4-methylideneoxolan-3-yl]methanol
• 化学式: C₁₃H₁₄O₄
• 分子量: 234.252
• InChiKey: FVICNTCGMNJRRL-GWCFXTLKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-exomethylene-3-(hydroxy)[(3,4-methylenedioxy)phenyl]methyltetrahydrofuran 在 2,6-二甲基吡啶 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Pd-catalyzed route to (±)-podophyllotoxin skeleton. Synthesis of the aryltetralin derivative

  摘要：

  A new Pd-catalyzed route to (+/-)-podophyllotoxin is disclosed, The strategy is based on an efficient organoaqueous reaction that diastereoselectivity introduces the C-4 hydroxyl group and the furan ring. Further functionalization led to all iododerivative. which was cyclized under optimized conditions either to the aryltetralin of (+/-)-podophyllotoxin or to a five-membered ring isomer. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00908-5
• 作为产物：
  描述：

  (E)-3-[(3,4-methylenedioxy)phenyl]prop-2-en-1-yl propargyl oxide 在 gold(III) chloride silver hexafluoroantimonate 、 水 、 三苯基膦 作用下， 以 1,4-二氧六环 为溶剂， 反应 24.0h， 以90%的产率得到4-exomethylene-3-(hydroxy)[(3,4-methylenedioxy)phenyl]methyltetrahydrofuran
  参考文献：
  名称：

  金催化的官能化烯炔的羟基和烷氧基环化

  摘要：

  描述了一种通用的 Au III 催化系统，用于 1,6-烯炔的有效羟基和烷氧基环化反应。该反应导致碳和杂环醇或醚的产率良好至极好。在AuCl 3 /AgSbF 6 /PPh 3 催化剂的存在下，在二恶烷-水或各种醇中在室温下进行环化。1,7-烯炔的羟基环化反应得到甲基酮或甲基酮和碳环醇的混合物。

  DOI：

  10.1055/s-2007-982570

文献信息

• Asymmetric Au-catalyzed domino cyclization/nucleophile addition reactions of enynes in the presence of water, methanol and electron-rich aromatic derivatives
  作者：Alexandre Pradal、Chung-Meng Chao、Maxime R. Vitale、Patrick Y. Toullec、Véronique Michelet

  DOI：10.1016/j.tet.2011.03.071

  日期：2011.6

  system is described for the asymmetric domino cyclization/functionalization reactions of functionalized 1,6-enynes in the presence of an external nucleophile. The use of (R)-4-MeO-3,5-(t-Bu)2-MeOBIHEP ligand associated with gold led to clean rearrangements implying the formal addition of an oxygen or carbon nucleophile to an alkene followed by a cyclization process. The enantiomeric excesses were highly

  描述了一种有效的Au（I）催化体系，用于在外部亲核试剂存在下官能化1,6-烯炔的不对称多米诺环化/官能化反应。与金缔合的（R）-4-MeO-3,5-（t - Bu）2 -MeOBIHEP配体的使用导致干净的重排，这意味着将氧或碳亲核体正式加成至烯烃，然后进行环化过程。对映体过量高度依赖于底物/亲核试剂的组合。在带有较大基团的基团（受阻的二酯和二砜）和受阻碳亲核试剂的情况下，可以获得很好的对映体过量，最高可达98％。
• Cycloisomerization of 1,6-enynes in organoaqueous medium: an efficient and eco-friendly access to furan derivatives. Synthesis of a key intermediate of podophyllotoxin
  作者：Jean-Christophe Galland、Sonia Dias、Monique Savignac、Jean-Pierre Genêt

  DOI：10.1016/s0040-4020(01)00368-4

  日期：2001.6

  The first cycloisomerization of enynes catalyzed by Pd(TPPTS)(3) catalyst in aqueous medium to give functionalized furans is described. This new reaction has been applied to the synthesis of podophyllotoxin analog. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Towards asymmetric Au-catalyzed hydroxy- and alkoxycyclization of 1,6-enynes
  作者：Chung-Meng Chao、Emilie Genin、Patrick Y. Toullec、Jean-Pierre Genêt、Véronique Michelet

  DOI：10.1016/j.jorganchem.2008.08.008

  日期：2009.2

  The efficiency of a Au(III)/chiral ligand system has been studied. The association of several chiral mono- and bidentate phosphanes with gold has been tested in the formal addition of an oxygen nucleophile to an alkene followed by a cyclization process, namely the hydroxycyclization reaction of 1,6-enynes. The use of ( R)-4-MeO-3,5-(t-Bu)(2)-MeOBIPHEP ligand led to clean cycloisomerizations and afforded the highest enantiomeric excesses. The enantiomeric excesses were highly dependant on the substrate/nucleophile combination. A P-31 NMR study of the catalytic species tends to prove that Au( III) catalyst may be reduced to Au( I) intermediate in the presence of phosphanes. (C) 2008 Elsevier B.V. All rights reserved.
• Gold-Catalyzed Hydroxy- and Alkoxycyclization of Functionalized Enynes
  作者：Jean-Pierre Genêt、Véronique Michelet、Emilie Genin、Lucie Leseurre、Patrick Toullec

  DOI：10.1055/s-2007-982570

  日期：2007.7

  A general Au III catalytic system is described for the efficient hydroxy- and alkoxycyclization reactions of 1,6-enynes. The reactions lead to carbo- and heterocyclic alcohols or ethers in good to excellent yields. The cyclizations are conducted in the presence of AuCl 3 /AgSbF 6 /PPh 3 catalyst in dioxane-water or various alcohols at room temperature. The hydroxycyclization reactions of 1,7-enynes

  描述了一种通用的 Au III 催化系统，用于 1,6-烯炔的有效羟基和烷氧基环化反应。该反应导致碳和杂环醇或醚的产率良好至极好。在AuCl 3 /AgSbF 6 /PPh 3 催化剂的存在下，在二恶烷-水或各种醇中在室温下进行环化。1,7-烯炔的羟基环化反应得到甲基酮或甲基酮和碳环醇的混合物。
• Pd-catalyzed route to (±)-podophyllotoxin skeleton. Synthesis of the aryltetralin derivative
  作者：Lise Charruault、Véronique Michelet、Jean-Pierre Genêt

  DOI：10.1016/s0040-4039(02)00908-5

  日期：2002.7

  A new Pd-catalyzed route to (+/-)-podophyllotoxin is disclosed, The strategy is based on an efficient organoaqueous reaction that diastereoselectivity introduces the C-4 hydroxyl group and the furan ring. Further functionalization led to all iododerivative. which was cyclized under optimized conditions either to the aryltetralin of (+/-)-podophyllotoxin or to a five-membered ring isomer. (C) 2002 Elsevier Science Ltd. All rights reserved.